Disazo dyestuffs



United States Patent OfiFice 2,722,527 Patented Nov. 1, 1955 2,722,527 DISAZO DYESTUFFS Walter Wehrii, Riehen, near Basel, and Jakob Benz,

Basel, Switzerland, assignors to Sandoz A. G., Basel,

Switzerland No Drawing. Application June 28, 1954, Serial No. 439,919 Claims priority, application Switzerland July 9, 1953 6 Claims. (Cl. 260-153) The present invention relates to substantive disazo dyestuffs.

Valuable substantive disazo dyestutfs are obtained by replacing, on the one hand, a halogen atom of a sixmembered triazine compound which contains at least two and at most three replaceable halogen atoms bound to carbon atoms, by the radical of the aminodisazo compound from diazotized 4-amino-l,1'-azobenzene-3,4- disulfonic acid and Z-amino--hydroxynaphthalene-7- sulfonic acid, which aminodisazo radical is coupled in ortho-position to the hydroxyl group, and, on the other hand, replacing the remaining halogen atom or one of the two remaining halogen atoms by the radical of an aminobenzene which is substituted by a Water-solubilizing group, such for example as the sulfonic acid group, the carboxyl group, a sulfonic acid amide group which may be substituted at the nitrogen atom, or an alkylsulfonyl group, and if desired replacing the third halogen atomif a third halogen atom is presentby the hydroxyl group or by a primary, secondary or tertiary amino group, the said replacement operations being carried out in any desired order of succession.

An alternative mode of procedure comprises coupling diazotized 4-amino-l,1'-azobenzene-3,4'-disulfonic acid with a triazine compound of the formula OH 2 (I) wherein x stands for methyl, phenyl, halogen, hydroxyl or a primary, secondary or tertiary amino group, and R stands for a radical of the benzene series containing a water-solubilizing group such as for example the sulfonic acid group, the carboxyl group, a sulfonic acid amide group which may be substituted at the nitrogen atom, or an alkylsulfonyl group. When x stands for halogen, this halogen atom may in the obtained disazo dyestutf be replaced by the hydroxyl group or by a primary, secondary or tertiary amino group.

Illustrative of six-membered triazine compounds containing at least two and at most three replaceable halogen atoms bound to carbon atoms, which may be used in carrying out the first aforedescribed process embodiment, are for example l-methyl-3,S-dichlorotriazine, l-phenyl- 3,5-dichlorotriazine, cyanuric bromide and, especially, cyanuric chloride. The reaction of the triazine compounds containing the replaceable halogen atoms is advantageously carried out in aqueous medium and in the presence of an acid-binding agent, such for example as lithiumor sodiumor potassium-hydroxide or -carbonate or -bicarbonate or -acetate.

The aminodisazo compound specified as starting compound in the first process embodiment can be very readily obtained by coupling diazotized 4-amino-1,1'-azobenzene- 3,4'-disulfonic acid with a Z-acylamino-5-hydroxynaphthalene-7-sulfonic acid in neutral to weakly acid medium,

separating the by-product which is coupled in the 8-position of the naphthalene nucleus, and then saponifying the acylamino group to the amino group.

The aminobenzenes substituted by a Water-solubilizing group, which are used as starting materials in the afore-' said first process embodiment and the residue of which is indicated as RNH- in Formula I, are advantageously chosen from the series of the aminobenzene sulfonic acids, aminobenzene carboxylic acids, aminobenzene sulfonic acid amides which may be further substituted by aliphatic, carbocyclic or heterocyclic radicals at the nitrogen atom of the sulfonic acid amide group, and aminoalkylsulfonylbenzenes. Preferred compounds in this category are l-aminobenzene-3-sulfonic acid, 1-aminobenzene-4-sulfonic acid, l-aminobenzene-Ii-carboxylic acid, l-aminobenzene-4-carboxylic acid, l-aminobenzene-3-sulfonic acid amide, l-aminobenzene-4-sulfonic acid amide, 1-amino-3-methylsulfonylbenzene, and 1- amino-4-methylsulfonylbenzene. Aminobenzenes which, in addition to the aforedefined water-solubilizing groups, also carry additional substituents, such for example as halogen or alkyl, are also suitable in preparing the dyestufis of the present invention. The water-solubilizing group facilitates the reaction of the aminobenzene with the triazine compound. Where the water-solubility of the aminobenzene is only slight, such compound can be added to the aqueous condensation mass in the form of a solution in a water-miscible organic solvent, such for example as acetone.

For the reaction with the optionally-present third halogen atom of the triazine compound, according to the first and second aforedescribed process embodiments, use may suitably be made of primary or secondary aliphatic amines which may be substituted by halogen or hydroxyl, or of primary or secondary carbocyclic or heterocyclic amines which, if desired, may be further substituted. Illustrative of such amines are for example the aforementioned aminobenzenes, and also methylamine, dimethylamine, ethylamine, 2-hydroxyethylamine, di-(2- hydroxy-ethyD-amiue, propylamine, 3-hydroxypropylamine, butylamine, amylamine, hexylamine, benzylamine, cyclohexylamine, morpholine, aminobenzene, 1-amino-3- chlorobenzene, l-amino 4 chlorobenzene, 1-amino-3- methylbenzene, l-amino 4 methylbenzene, 1-amino-4- methoxybenzene, l-amino 4 acetylaminobenzene, 1- amino-dimethylbenzenes, N-rnethylaminobenzene, N-ethylaminobenzene and lor Z-aminonaphthalenesulfonic acids. The here-enumerated amines also occur as residues in Formula I when x has the corresponding significance.

The triazine compounds of Formula I, which form the basis of the aforedescribed second process embodiment, are obtained by replacing, on the one hand, one halogen atom of a six-membered triazine compound, which contains at least two and at most three replaceable halogen atoms bound to carbon atoms, by the Z-amino-S-hydroxynaphthalene-7-sulfonic acid radical and, on the other hand, replacing the remaining halogen atom or one of the remaining halogen atoms by the radical of an aminobenzene which is substituted by a water-solubilizing group, and if desired replacing the third halogen atomif a third halogen atom is present-by hydroxyl, amino or the radical of a primary or secondary aliphatic, carbocyclic or heterocyclic amine which may be substituted, the replacement operations being carried out in any desired order of succession.

The substantive disazo dyestuffs according to the present invention correspond to the formula SOaH OH :1: (II) 2,722,527 3 4 wherein x and R have the previously indicated signifitriazine compound obtained by the stepwise condensation, cances. These dyestuffs are distinguished by the vividafter the manner of the preceding paragraph, of a cyness of the shade of their dyeings. They dye cotton and anuric trihalide with 2-amino-5-hydroxynaphthalene-7- fibers of regenerated cellulose in scarlet to red shades of sulfonic acid, 1-aminobenzene-3-sulfonic acid amide and good fastness to light, to washing and to perspiration. 5 aminobenzene, and separating the by-product which is The following examples set forth typical representacoupled in the 8-position. tive embodiments of the invention, and are intended to be Dyestuffs with similar properties are obtained when in wholly illustrative and not at all limitative in character. either or both of the afore-described processes the 20 In the said examples, the parts and the percentages are parts of the aminobenzene are replaced by the equivalent by weight. The temperatures are degrees Centigrade. 10 quantity of cyclohexylamine, di-(2-hydroxyethyl)-amine,

methylamine, octylamine, morpholine, 1-amino-4-meth- EXAMPLE 1 oxybenzene, l-amino-4-ethylbenzene or 1-amino-4-meth- 60.7 parts of aminodisazo compoundobtained by ylsulfonylbenzene. Thus, the disazo dyestuff wherein coupling diazotized 4-amino-1,1-azobenzene-3,4'-disulaminobenzene is replaced by 1amino-4-methoxybenzene,

fonic acid with 2-acetylamino-S-hydroxynaphthalene-7- corresponds to the formula EXAMPLE 2 A neutral solution of 17.3 parts of l-aminobenzene- 4-sulfonic acid in 80 parts of water are run, at 0-3 and in the course of 30 minutes, into a suspension of 18.4 parts of cyanuric chloride in 200 parts of water. By the dropwise addition of a dilute aqueous sodium car bonate solution, care is taken that the reaction of the condensation medium remains weakly acid throughout. The mass is stirred for another hour at 0-3. Then the suspension is heated to 40; at this temperature and in the course of 30 minutes, there is added to the suspension a neutral solution of 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid in 400 parts of water, the reaction being kept weakly acid by the dropwise addition of dilute aqueous sodium carbonate solution. The mass is then stirred for 30 more minutes under the indicated conditions. Finally, parts of aminobenzene are added and the reaction mass is then heated to sulfonic acid in weakly acid medium, separating the byproduct which is coupled in the 8-position, and then saponifying the acetylamino group to the amino groupare dissolved in 400 parts with the addition of alkali to maintain the solution neutral. The resultant solution is slowly added to a suspension of 18.4 parts of cyanuric chloride in 300 parts of ice water, and the condensation mass is stirred for 1 /2 to 2 hours at 03, the reaction of the mass being maintained weakly acid throughout this operation by the dropwise addition of a dilute aqueous sodium carbonate solution. The suspension of the thusformed primary condensation product is heated to 25, after which there is added a solution-heated to 80-of 17.2 parts of l-aminobenzene-3-sulfonic acid amide in 150 parts of water. The mass is then warmed to for one hour, care being taken to maintain the pH of the 45 mass at all times between 5.5 and 6.5 by the dropwise addition of a dilute sodium carbonate solution. To the resultant solution of the now-present secondary condenfor 2 hours The reaction mass is then adjusted Sation Product 20 Parts of amlnobenzene are f the to Weak alkalinity by the addition of sodium carbonate, mass heated to for 11/2, P and then sohmon of after which it is filtered and the filter cake washed with 10 Parts of Sodium hydroxide 111 30 Parts of Water added dilute aqueous sodium chloride solution. 5 8.0 parts of to the thus-obtained solution of the resultant ternary conh thus obtained pure ternary condensation product are densation product. The disazo dyestuff is precipitated dissolved in 600 parts of water, the solution being mainby the addition of sodium chloride to the alkaline contained neutral by the addition of sodium carbonate. densation solution, after which the precipitated disazo After the addition of 10 parts of sodium bicarbonate, the dyestutf is filtered olf and is dried. It corresponds to the diazo compound of 35.7 parts of 4-arnino-l,1-azobenformula zene-3,4-disulfonic acid is added to the solution, and

N Hols NH,/ i-NH HO:S-C N=N =N SOQNH:

and is a red powder which dyes cotton and fibers of re- 70 the mass is stirred until the coupling which ensues is generated cellulose in vivid red shades of good fastness ended. The reaction mass is then heated to 80, to light, to washing and to perspiration. the produced disazo dyestuff is salted out and filtered off.

The identical product is obtained by coupling di- By reprecipitation, the said disazo dyestuff is completeazotized 4-amino-l,l'-azobenzene-3,4'-disulfonic acid in ly freed from a blue by-product, after which the disazo weakly acid, neutral or weakly alkaline medium with the 7 5 dyestulf is dried. It corresponds to the formula and is a red powder which dyes cotton and fibers of regenerated cellulose in vivid red shades with good fast- (1) (2) (3) y (4) ness to light, to washing, and to perspiration. The Shade oi identical dyestuif is obtained by condenslng one mol of Example Dyeingv N RNH the am1nod1sazo dyestufi dlsclosed in Example 1, one mol v Cotton of l-am1n0benzene-4-sulfon1c acid and one mol of aminobenzene with one mol of cyanuric chloride 7 ..do 1-am1no-4-meth lbenred. The following table exemplifies additional disazo dye-. zenHe, y

8 ..do 1 red. stuffs yvhlch can be prepared according to one of the 9 "do di (2, hydmyethy1 ML foregomg examples. The dyestufis correspond to Ford amgicl. d mula II, supra. The table sets forth the amine correfi Te 11 do 1-am1no-4-methoxyred. spondmg to the RNH residue, and the substituents b nzene. corresponding to the symbol x. Where x stands for the 12 'gfi fgi ffgg' iify j ammbemene residue of an amine, the amine itself is recited for the amide. sake of simplicity. The last column of the table finally 13 igfifli ffifgggj sets forth the shade of the respective dyeings on cotton. amide.

14 1-amino-3-methyl-su1- aminobenzene. red.

fonylbenzene. Table 15 l-aminobenzene-ii-suldo red. ionic acid-dimethyb amide. 16 1-amino-3-phenyl-suldo red. (1) (2) (3) (4) fonylbenzene.

17 1-amrnobenzene-3-sul- N-methylamino-bcnred. Shade of ionic acid. zene. Example Dyeing 18 l-aminobenzene-i-sulaminobenzene red.

I on fonic acid-(2-hy- Cotton droxy)-ethylamidet 19 l-aminobenzene--suldo red.

ionic acid-(W 08i- 3 l-aminobenzenel-caraminobenzene red. boxy)-D Y boxylic acid. 20 l-armnobenzene-i-sull-aminoi-methyl-sulred. 4 l-aminobenzene-ii-carcyclohexylamine red. i011!!! acid amldeiollylbelllene.

boxylic acid. 5 1-arninobenzene-3-suloctylaminem -tred.

acld- Representative examples are 12 and 14. The for- 6 l-aminobenzenei-suldo red.

ionic acid amide, mulae of the thus-obtained dyestuffs are:

EXAMPLE 12 EXAMPLE 14.

IIIH

7 EXAMPLE 21 Having thus disclosed the invention, what is claimed is: 1 part of the disazo dyestufi obtained according to 1. A substantive disazo dyestufi which corresponds to Example 2 is dissolved in 3000 parts of water; to this the formula solution 5 parts of Glaubers salt are added. The resultant dyebath is heated to 50 and, at this temperature, 100 wherein x stands for a member selected from the group parts of cotton are entered. The dyebath is then heated to consisting of primary amino, secondary amino and tertiary 95 in the course of -20 minutes, and is maintained at 15 amino groups and R stands for a radical of the benzene this temperature for 15 minutes. 5-15 additional parts series containingawater-solubilizing group. of Glaubers salt are then added and the dyeing con- 2. The substantive disazo dyestuff corresponding to the tinned at 95 for about minutes. The bath is then formula 1 :11 H NH allowed to cool to and the dyed material withdrawn, 3. The substantive disazo dyestuff corresponding to the thoroughly rinsed and dried. There is thus obtained a formula H038 NH(IJ (IJNHQ N N HO:S 3N=N- 'N= somm 403E H ILIH OCH:

dyeing of outstanding fastness to light and of good fastness 4. The substantive disazo dyestuff corresponding to the to wet treatments. formula 50:11 OH NH Fibers of regenerated cellulose can be dyed in similar 5. The substantive disazo dyestuff corresponding to the manner. formula.

SOaH H NH 6. The substantive disazo dyestufif corresponding to the formula No references cited. 

1. A SUBSTANTIVE DISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 